Oxidation dyeing composition for keratin fibers comprising 2-chloro-6-methyl-3-aminophenol, an oxidation base and an additional coupler, and dyeing method

ABSTRACT

The subject-matter of the present invention is a composition for the oxidation dyeing of keratinous fibers, in particular of human keratinous fibers, such as hair, comprising 2-chloro-6-methyl-3-aminophenol as coupler, in combination with at least one suitably selected oxidation base and at least one additional coupler chosen from suitably selected meta-aminophenols and meta-phenylenediamines, and the dyeing process employing this composition with an oxidizing agent.

The subject-matter of the present invention is a composition for theoxidation dyeing of keratinous fibres, in particular of human keratinousfibres, such as hair, comprising 2-chloro-6-methyl-3-aminophenol ascoupler, in combination with at least one suitably selected oxidationbase and at least one additional coupler chosen from suitably selectedmeta-aminophenols and meta-phenylenediamines, and the dyeing processemploying this composition with an oxidizing agent.

It is known to dye keratinous fibres and in is particular human hairwith dyeing compositions comprising oxidation dye precursors, inparticular ortho- or para-phenylenediamines, ortho- orpara-aminophenols, or heterocyclic compounds, such as pyrimidinederivatives, generally known as oxidation bases. Oxidation dyeprecursors or oxidation bases are colourless or weakly colouredcompounds which, in combination with oxidizing substances, can giverise, by an oxidative coupling process, to coloured and colouringcompounds.

It is also known that it is possible to vary the shades obtained withoxidation bases by combining them with suitably chosen couplers orcolouring modifiers, it being possible for the latter in particular tobe chosen from aromatic meta-diamines, meta-aminophenols, meta-diphenolsand certain heterocyclic compounds.

The variety of the molecules involved as oxidation bases and couplersmakes it possible to obtain a rich palette of colours.

The so-called “permanent” colouring obtained by virtue of theseoxidation dyes has, however, to satisfy a certain number ofrequirements. Thus, it must be without disadvantage toxicologically andit must make it possible to obtain shades with the desired intensity andbehave well in the face of external agents (light, bad weather, washing,permanent waving, perspiration or rubbing).

The dyes must also make it possible to cover white hair and, finally, beas non-selective as possible, that is to say make it possible to obtainthe smallest possible difference in colouring along the same keratinousfibre, which can in fact be differently sensitized (i.e. damaged)between its tip and its root.

Provision has already been made, in particular in German PatentApplication DE 3,016,008, for compositions for the oxidation dyeing ofkeratinous fibres comprising, as coupler,2-chloro-6-methyl-3-aminophenol or 2-methyl-5-chloro-3-aminophenol incombination with oxidation bases conventionally used for oxidationdyeing, such as, for example, certain para-phenylenediamines orpara-aminophenols. However, such compositions are not entirelysatisfactory, in particular from the viewpoint of the behaviour of thecolourings obtained with respect to various attacks which hair can besubjected to and in particular with respect to shampoos and permanentdeformations.

Provision has also been made, in Patent Applications WO 96/15765 and WO96/15766, for compositions for the oxidation dyeing of keratinous fibrescomprising the specific combination of 2-chloro-6-methyl-3-aminophenolas coupler, of a specific oxidation base, such as2-(R-hydroxyethyl)-para-phenylenediamine or 2-aminomethyl-4-aminophenol,and of a coupler, such as, for example, 2-methyl-5-aminophenol orresorcinol. However, such compositions are not entirely satisfactoryeither, in particular from the viewpoint of the selectivity of thecolourings obtained.

The Applicant Company has now just discovered that it is possible toobtain powerful novel dyes which are particularly resistant to thevarious attacks which hair can be subjected to by combining2-chloro-6-methyl-3-aminophenol, at least one suitably selectedoxidation base and at least one coupler chosen from suitably selectedmeta-aminophenols and meta-phenylenediamines.

This discovery is at the basis of the present invention.

The first subject-matter of the invention is therefore a composition forthe oxidation dyeing of keratinous fibres and in particular of humankeratinous fibres, such as hair, characterized in that it comprises, ina medium appropriate for dyeing:

2-chloro-6-methyl-3-aminophenol and/or at least one of its additionsalts with an acid, as first coupler;

at least one oxidation base;

and at least one additional coupler chosen from meta-aminophenols andmeta-phenylenediamines; it being understood that the said compositiondoes not simultaneously include 2-(β-hydroxyethyl)-para-phenylenediamineand 2-methyl-5-aminophenol.

The oxidation dyeing composition in accordance with the invention makesit possible to obtain powerful colourings with varied shades which arenot very selective and which exhibit excellent properties of resistanceboth with respect to atmospheric agents, such as light and bad weather,and with respect to perspiration and various treatments which hair canbe subjected to (shampoos, permanent deformations). These properties areparticularly noteworthy, in particular as regards the low selectivity ofthe colourings obtained.

The oxidation bases which can be used in the dyeing compositions inaccordance with the invention are preferably chosen frompara-phenylenediamines, double bases, para-aminophenols,ortho-aminophenols and heterocyclic oxidation bases.

Mention may in particular be made, among the para-phenylenediamineswhich can be used as oxidation bases in the dyeing compositions inaccordance with the invention, of the compounds of following formula (I)and their addition salts with an acid:

in which:

R₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedby a nitrogenous, phenyl or 4′-aminophenyl group;

R₂ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedby a nitrogenous group;

R₃ represents a hydrogen atom, a halogen atom, such as a chlorine,bromine, iodine or fluorine atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₁-C₄ hydroxyalkoxy radical, a C₁-C₄acetylaminoalkoxy radical, a C₁-C₄ mesylaminoalkoxy radical or a C₁-C₄carbamoylaminoalkoxy radical;

R₄ represents a hydrogen or halogen atom or a C₁-C₄ alkyl radical.

Mention may in particular be made, among the nitrogenous groups of theabove formula (I), of the amino, mono(C₁-C₄)alkylamino,di(C₁-C₄)alkylamino, tri(C₁-C₄)alkylamino, monohydroxy(C₁-C₄)alkylamino,imidazolinium and ammonium radicals.

Mention may more particularly be made, among the para-phenylenediaminesof above formula (I), of para-phenylenediamine, para-toluylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-3-methylaniline,4-amino-3-chloro-N,N-bis(β-hydroxyethyl)aniline,2-(β-hydroxyethyl)-para-phenylenediamine,2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-(β-hydroxyethyloxy)-para-phenylenediamine,2-(β-acetylaminoethyloxy)-para-phenylenediamines,N-(β-methoxyethyl)amino-para-phenylenediamine and their addition saltswith an acid.

Preference is very particularly given, among the para-phenylenediaminesof above formula (I), to para-phenylenediamine, para-toluylenediamine,2-isopropyl-para-phenylenediamine,2-(β-hydroxyethyl)-para-phenylenediamine, 2-(β-hydroxyethyloxy)-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,2-chloro-para-phenylenediamine,2-(β-acetylaminoethyloxy)-para-phenylenediamine and their addition saltswith an acid.

According to the invention, double bases is understood to mean thecompounds comprising at least two aromatic nuclei on which are carriedamino and/or hydroxyl groups.

Mention may in particular be made, among the double bases which can beused as oxidation bases in the dyeing compositions in accordance withthe invention, of the compounds corresponding to the following formula(II) and their addition salts with an acid:

in which:

Z₁ and Z₂, which are identical or different, represent a hydroxyl or—NH₂ radical which can be substituted by a C₁-C₄ alkyl radical or by aconnecting arm Y;

the connecting arm Y represents a linear or branched alkylene chaincomprising from 1 to 14 carbon atoms which can be interrupted orterminated by one or more nitrogenous groups and/or by one or moreheteroatoms, such as oxygen, sulphur or nitrogen atoms, and which isoptionally substituted by one or more hydroxyl or C₁-C₆ alkoxy radicals;

R₅ and R₆ represent a hydrogen or halogen atom, a C₁-C₄ alkyl radical, aC₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, aC₁-C₄ aminoalkyl radical or a connecting arm Y;

R₇, R₈, R₉, R₁₀, R₁₁ and R₁₂, which are identical or different,represent a hydrogen atom, a connecting arm Y or a C₁-C₄ alkyl radical;

it being understood that the compounds of formula (II) only comprise asingle connecting arm Y per molecule.

Mention may in particular be made, among the nitrogenous groups of theabove formula (II), of the amino, mono(C₁-C₄)alkylamino,di(C₁-C₄)alkylamino, tri(C₁-C₄)alkylamino, monohydroxy(C₁-C₄)alkylamino,imidazolinium and ammonium radicals.

Mention may more particularly be made, among the double bases of aboveformula (II), of N,N′-bis (β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino propanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis (4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)-tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-diethyl-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane and their addition saltswith an acid.

N,N′-Bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane or one of their additionsalts with an acid are particularly preferred among these double basesof formula (II).

Mention may in particular be made, among the para-aminophenols which canbe used as oxidation bases in the dyeing compositions in accordance withthe invention, of the compounds corresponding to the following formula(III) and their addition salts with an acid:

in which:

R₁₃ represents a hydrogen or halogen atom, a C₁-C₄ alkyl radical, aC₁-C₄ monohydroxyalkyl radical, a (C₁-C₄)alkoxy(C₁-C₄) alkyl radical, aC₁-C₄ aminoalkyl radical or a hydroxy(C₁-C₄)alkylamino-(C₁-C₄)alkylradical,

R₁₄ represents a hydrogen or halogen atom, a C₁-C₄ alkyl radical, aC₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, aC₁-C₄ aminoalkyl radical, a C₁-C₄ cyanoalkyl radical or a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical,

it being understood that at least one of the R₁₃ or R₁₄ radicalsrepresents a hydrogen atom.

Mention may more particularly be made, among the para-aminophenols ofabove formula (III), of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-2-methylphenol, 4-amino-2-(hydroxymethyl)phenol,4-amino-2-(methoxymethyl)phenol, 4-amino-2-(aminomethyl)phenol,4-amino-2-[(β-hydroxyethyl)aminomethyl]phenol, 4-amino-2-fluorophenoland their addition salts with an acid.

Mention may more particularly be made, among the ortho-aminophenolswhich can be used as oxidation bases in the dyeing compositions inaccordance with the invention, of 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 5-acetamido-2-aminophenol and their additionsalts of an acid.

Mention may more particularly be made, among the heterocyclic baseswhich can be used as oxidation bases in the dyeing compositions inaccordance with the invention, of pyridine derivatives, pyrimidinederivatives, pyrazole derivatives, pyrazolopyrimidine derivatives andtheir addition salts with an acid.

Mention may more particularly be made, among pyridine derivatives, ofthe compounds disclosed, for example, in Patents GB 1,026,978 and GB1,153,196, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridineand their addition salts with an acid.

Mention may more particularly be made, among pyrimidine derivatives, ofthe compounds disclosed, for example, in German Patent DE 2,359,399 orJapanese Patents JP 88-169,571 and JP 91-333,495 or Patent ApplicationWO 96/15765, such as 2,4,5,6-tetraaminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and theiraddition salts with an acid.

Mention may more particularly be made, among pyrazole derivatives, ofthe compounds disclosed in Patents DE 3,843,892 and DE 4,133,957 andPatent Applications WO 94/08969, WO 94/08970, FR-A-2,733,749 and DE 19543 988, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole,4,5-diamino-1-(4,-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-(hydroxymethyl)pyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-amino-ethyl)amino-1,3-dimethylpyrazole,3,4,5-triamino-pyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-(methylamino)pyrazole,3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole and their additionsalts with an acid.

Mention may more particularly be made, among pyrazolopyrimidinederivatives, of the pyrazolo [1,5-a]pyrimidines of following formula(IV), their addition salts with an acid or with a base and theirtautomeric forms, when a tautomeric equilibrium exists:

in which:

R₁₅, R₁₆, R₁₇ and R₁₈, which are identical or different, denote ahydrogen atom, a C₁-C₄ alkyl radical, an aryl radical, a C₁-C₄hydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ aminoalkyl radical (it beingpossible for the amine to be protected by an acetyl, ureido or sulphonylradical), a (C₁-C₄)alkylamino(C₁-C₄)alkyl radical, adi[(C₁-C₄)alkyl]amino(C₁-C₄)alkyl radical (it being possible for thedialkyl radicals to form a carbonaceous ring or a heterocycle with 5 or6 ring members) or a hydroxy(C₁-C₄)alkyl- ordi[hydroxy(C₁-C₄)alkyl]amino(C₁-C₄)alkyl radical;

the X radicals, which are identical or different, denote a hydrogenatom, a C₁-C₄ alkyl radical, an aryl radical, a C₁-C₄ hydroxyalkylradical, a C₂-C₄ polyhydroxyalkyl radical, a C₁-C₄ aminoalkyl radical, a(C₁-C₄)alkylamino(C₁-C₄)alkyl radical, adi[(C₁-C₄)alkyl]amino(C₁-C₄)alkyl radical (it being possible for thedialkyls to form a carbonaceous ring or a heterocycle with 5 or 6 ringmembers), a hydroxy(C₁-C₄)alkyl- ordi[hydroxy(C₁-C₄)alkyl]amino(C₁-C₄)alkyl radical, an amino radical, a(C₁-C₄)alkyl- or di[(C₁-C₄)alkyl]amino radical, a halogen atom, acarboxylic acid group or a sulphonic acid group;

i has the value 0, 1, 2 or 3;

p has the value 0 or 1;

q has the value 0 or 1;

n has the value 0 or 1;

with the proviso that:

the sum p+q is other than 0;

when p+q is equal to 2, then n has the value 0 and the NR₁₅R₁₆ andNR₁₇R₁₈ groups occupy the (2,3), (5,6), (6,7), (3,5) or (3,7) positions;

when p+q is equal to 1, then n has the value 1 and the NR₁₅R₁₆ (orNR₁₇R₁₈) group and the OH group occupy the (2,3), (5,6), (6,7), (3,5) or(3,7) positions.

When the pyrazolo[1,5-a]pyrimidines of above formula (IV) are such thatthey comprise a hydroxyl group on one of the 2, 5 or 7 positions α to anitrogen atom, there exists a tautomeric equilibrium represented, forexample, by the following scheme:

Mention may in particular be made, among the pyrazolo[1,5-a]pyrimidinesof above formula (IV), of:

pyrazolo[1,5-a]pyrimidine-3,7-diamine;

2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

pyrazolo[1,5-a]pyrimidine-3,5-diamine;

2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;

3-aminopyrazolo[1,5-a]pyrimidin-7-ol;

3-aminopyrazolo[1,5-a]pyrimidin-5-ol;

2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;

2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;

2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl) (2-hydroxyethyl)amino]ethanol;

2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl) (2-hydroxyethyl)amino]ethanol;

5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;

and their addition salts and their tautomeric forms, when there exists atautomeric equilibrium.

The pyrazolo[1,5-a]pyrimidines of above formula (IV) can be prepared bycyclization from an aminopyrazole according to the syntheses disclosedin the following references:

EP 628,559, Beiersdorf-Lilly

R. Vishdu and H. Navedul, Indian J. Chem., 34b (6), 514, 1995.

N. S. Ibrahim, K. U. Sadek and F. A. Abdel-Al, Arch. Pharm., 320, 240,1987.

R. H. Springer, M. B. Scholten, D. E. O'Brien, T. Novinson, J. P. Millerand R. K. Robins, J. Med. Chem., 25, 235, 1982.

T. Novinson, R. K. Robins and T. R. Matthews, J. Med. Chem., 20, 296,1977.

U.S. Pat. No. 3,907,799, ICN Pharmaceuticals.

The pyrazolo[1,5-a]pyrimidines of above formula (IV) can also beprepared by cyclization from hydrazine according to the synthesesdescribed in the following references:

A. McKillop and R. J. Kobilecki, Heterocycles, 6 (9), 1355, 1977.

E. Alcade, J. De Mendoza, J. M. Marcia-Marquina, C. Almera and J.Elguero, J. Heterocyclic Chem., 11 (3), 423, 1974.

K. Saito, I. Hori, M. Higarashi and H. Midorikawa, Bull. Chem. Soc.Japan, 47 (2), 476, 1974.

Mention may more particularly be made, among the meta-aminophenols whichcan be used as additional coupler in the dyeing compositions inaccordance with the invention, of the compounds of following formula (V)and their addition salts with an acid:

in which:

R₁₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical,

R₂₀ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine or fluorine,

R₂₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical or a C₂-C₄ polyhydroxyalkoxyradical.

Mention may more particularly be made, among the meta-aminophenols ofabove formula (V), of 5-amino-2-methoxyphenol,5-amino-2-(β-hydroxyethyloxy)phenol, 5-amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 5-amino-4-chloro-2-methylphenol,5-amino-2,4-dimethoxyphenol, 5-(γ-hydroxypropylamino)-2-methylphenol andtheir addition salts with an acid.

Mention may more particularly be made, among the meta-phenylenediamineswhich can be used as additional coupler in the dyeing compositions inaccordance with the invention, of the compounds of following formula(VI) and their addition salts with an acid:

in which:

R₂₂ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical;

R₂₃ and R₂₄, which are identical or different, represent a hydrogenatom, a C₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkoxy radical or aC₂-C₄ polyhydroxyalkoxy radical;

R₂₅ represents a hydrogen atom, a C₁-C₄ alkoxy radical, a C₁-C₄aminoalkoxy radical, a C₁-C₄ monohydroxyalkoxy radical, a C₂-C₄polyhydroxy-alkoxy radical or a 2,4-diaminophenoxyalkoxy radical.

Mention may more particularly be made, among the meta-phenylenediaminesof above formula (VI), of meta-phenylenediamine,3,5-diamino-1-ethyl-2-methoxybenzene,3,5-diamino-2-methoxy-1-methylbenzene, 2,4-diamino--ethoxybenzene,1,3-bis(2,4-diaminophenoxy)propane, bis(2,4-diaminophenoxy)methane,1-(β-aminoethyloxy)-2,4-diaminobenzene,2-amino-1-(β-hydroxyethyloxy)-4-(methylamino)benzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-5-(β-hydroxy-ethyloxy)-1-methylbenzene,2,4-diamino-1-(β,γ-dihydroxypropyloxy)benzene,2,4-diamino-1-(β-hydroxy-ethyloxy) benzene,2-amino-4-N-(β-hydroxyethyl)amino-1-methoxybenzene and their additionsalts with an acid.

2Chloro-6-methyl-3-aminophenol and/or the addition salt or salts with anacid preferably represent from 0.0001 to 5% by weight approximately tothe total weight of the dyeing composition and more preferably stillfrom 0.005 to 3% by weight approximately of this weight.

The oxidation base or bases in accordance with the invention preferablyrepresent from 0.0005 to 12% by weight approximately of the total weightof the dyeing composition and more preferably still from 0.005 to 6% byweight approximately of this weight.

The additional coupler or couplers in accordance with the inventionpreferably represent from 0.0001 to 5% by weight approximately of thetotal weight of the dyeing composition and more preferably still from0.005 to 3% by weight approximately of this weight.

The dyeing compositions in accordance with the invention canadditionally comprise one or more direct dyes, in particular formodifying the shades or enriching them with highlights.

The addition salts with an acid which can be used in the context of thedyeing compositions of the invention (oxidation bases and couplers) aregenerally chosen in particular from hydrochlorides, hydrobromides,sulphates and tartrates, lactates and acetates.

The medium appropriate for dyeing (or vehicle) is generally composed ofwater or of a mixture of water and of at least one organic solvent, inorder to dissolve the compounds which would not be sufficiently solublein water. Mention may be made, for example, as organic solvent, of lowerC₁-C₄ alkanols, such as ethanol and isopropanol, glycerol, glycols andglycol ethers, such as 2-butoxyethanol, propylene glycol, propyleneglycol monomethyl ether, diethylene glycol monoethyl ether anddiethylene glycol monomethyl ether, and aromatic alcohols, such asbenzyl alcohol or phenoxyethanol, the analogous products and theirmixtures.

The solvents can be present in proportions preferably of between 1 and40% by weight approximately with respect to the total weight of thedyeing composition and more preferably still between 5 and 30% by weightapproximately.

The pH of the dyeing composition in accordance with the invention isgenerally between 3 and 12 approximately and more preferably stillbetween 5 and 11 approximately. It can be adjusted to the desired valueby means of acidifying or basifying agents commonly used in dyeingkeratinous fibres.

Mention may be made, among acidifying agents, by way of example, ofinorganic or organic acids, such as hydrochloric acid, orthophosphoricacid, carboxylic acids, such as tartaric acid, citric acid or lacticacid, or sulphonic acids.

Mention may be made, among basifying agents, by way of example, ofaqueous ammonia, alkaline carbonates, alkanolamines, such as mono-, di-and triethanolamines, and their derivatives, sodium hydroxide, potassiumhydroxide and the compounds of following formula (VII):

in which R is a propylene residue optionally substituted by a hydroxylgroup or a C₁-C₄ alkyl radical; and R₂₆, R₂₇, R₂₈ and R₂₉, which areidentical or different, represent a hydrogen atom or a C₁-C₄ alkyl orC₁-C₄ hydroxyalkyl radical.

The dyeing composition according to the invention can also includevarious adjuvants conventionally used in hair dyeing compositions, suchas anionic, cationic, non-ionic, amphoteric or zwitterionicsurface-active agents or their mixtures, anionic, cationic, non-ionic,amphoteric or zwitterionic polymers or their mixtures, inorganic ororganic thickening agents, antioxidizing agents, penetration agents,sequestering agents, fragrances, buffers, dispersing agents,conditioning agents, such as, for example, silicones, which are volatileor non-volatile and modified or unmodified, film-forming agents,ceramides, preserving agents or opacifying agents.

Of course, a person skilled in the art will take care to choose this orthese optional additional compound or compounds so that the advantageousproperties intrinsically attached to the dyeing composition inaccordance with the invention are not, or not substantially,detrimentally affected by the envisaged addition or additions.

The dyeing composition according to the invention can be provided invarious forms, such as in the form of liquids, creams or gels, or in anyother form appropriate for carrying out dyeing of keratinous fibres andin particular of human hair.

Another subject-matter of the invention is a process for dyeingkeratinous fibres and in particular human keratinous fibres, such ashair, employing the dyeing composition as defined above.

According to this process, the dyeing composition as defined above isapplied to the fibres, the colour being developed at acidic, neutral oralkaline pH using an oxidizing agent which is added only at the time ofuse to the dyeing composition or which is present in an oxidizingcomposition applied simultaneously or sequentially in a separatefashion.

According to a particularly preferred embodiment of the dyeing processaccording to the invention, the dyeing composition described above ismixed, at the time of use, with an oxidizing composition comprising, ina medium appropriate for dyeing, at least one oxidizing agent present inan amount sufficient to develop a colouring. The mixture obtained issubsequently applied to the keratinous fibres and is left to stand for 3to 50 minutes approximately, preferably 5 to 30 minutes approximately,after which the hair is rinsed, washed with a shampoo, rinsed again anddried.

The oxidizing agent present in the oxidizing composition as definedabove can be chosen from oxidizing agents conventionally used for theoxidation dyeing of keratinous fibres and among which may be mentionedhydrogen peroxide, urea hydrogen peroxide, alkali metal bromates,persalts, such as perborates and persulphates, or peracids. Hydrogenperoxide is particularly preferred.

The pH of the oxidizing composition including the oxidizing agent asdefined above is such that, after mixing with the dyeing composition,the pH of the resulting composition applied to keratinous fibrespreferably varies between 3 and 12 approximately and more preferablystill between 5 and 11. It is adjusted to the desired value by means ofacidifying or basifying agents commonly used in dyeing keratinous fibresand as defined above.

The oxidizing composition as defined above can also include variousadjuvants conventionally used in hair dyeing compositions and as definedabove.

The composition which is finally applied to keratinous fibres can beprovided in various forms, such as in the form of liquids, creams orgels, or in any other form appropriate for carrying out dyeing ofkeratinous fibres and in particular of human hair.

Another subject-matter of the invention is a dyeing multi-compartmentdevice or kit or any other packaging system with several compartments, afirst compartment of which includes the dyeing composition as definedabove and a second compartment of which includes the oxidizingcomposition as defined above. These devices can be equipped with a meansallowing the desired mixture to be deposited on the hair, such as thedevices disclosed in Patent FR-2,586,913 on behalf of the ApplicantCompany.

The examples which follow are intended to illustrate the inventionwithout, for all that, limiting the scope thereof.

EXAMPLES Comparative Dyeing Examples 1 and 2

The following dyeing compositions in accordance with the invention wereprepared (contents in grams):

EXAMPLE 1 2(*) 2-Chloro-6-methyl-3-aminophenol (coupler) 1.17 1.172-(β-Hydroxyethyloxy)-para-phenylenediamine 1.8  — dihydrochloride(oxidation base) 2-(β-Hydroxyethyl)-para-phenylenediamine — 1.68dihydrochloride (oxidation base) 2-Methyl-5-aminophenol (coupler) 0.050.05 Common dyeing vehicle (**) (**) Demineralized water, q.s. for 100 g100 g (*): Example not forming part of the invention (**) Common dyeingvehicle: Oleyl alcohol polyglycerolated with 4.0 g 2 mol of glycerolOleyl alcohol polyglycerolated with 5.69 g A.M. 4 mol of glycerolcomprising 78% of active materials (A.M.) Oleic acid 3.0 g Oleylaminewith 2 mol of ethylene 7.0 g oxide, sold under the tradename EthomeenO12 ® by the company Akzo Diethylaminopropyl 3.0 g A.M.laurylaminosuccinamate, sodium salt, comprising 55% of A.M. Oleylalcohol 5.0 g Oleic acid diethanolamide 12.0 g Propylene glycol 3.5 gEthyl alcohol 7.0 g Dipropylene glycol 0.5 g Propylene glycol monomethylether 9.0 g Sodium metabisulphite as an aqueous 0.455 g A.M. solutioncomprising 35% of A.M. Ammonium acetate 0.8 g Antioxidizing agent,sequestering q.s. agent Fragrance, preserving agent q.s. Aqueous ammoniacomprising 20% of 10.0 g NH₃

At the time of use, each above dyeing composition was mixed with half anamount by weight of an oxidizing composition composed of a 10-volumeaqueous hydrogen peroxide solution (3% by weight).

Each resulting composition was applied for 30 minutes to locks ofnatural grey hair comprising 90% of white hairs and to locks of permedgrey hair comprising 90% of white hairs. The locks of hair weresubsequently rinsed, washed with a standard shampoo and then dried.

The colour of each lock of hair dyed with the compositions 1 and 2 wasevaluated in the Munsell system by means of a CM 2002 Minolta®calorimeter.

According to the Munsell notation, a colour is defined by the expressionH V/C, in which the three parameters respectively denote the tint or Hue(H), the intensity or Value (V) and the purity or Chromaticity (C), theoblique stroke in this expression being simply a convention and notindicating a ratio.

For each composition, the difference between the colour of the lock ofnatural grey hair and the colour of the lock of permed grey hair wascalculated by applying the Nickerson formula:

ΔE=0.4C ₀ ΔH+6ΔV+3ΔC

as described, for example, in “Couleur, Industrie et Technique” [Colour,Industry and Technology], pages 14-17, Vol. No. 5, 1978.

In this formula, ΔE represents the difference in colour between twolocks, ΔH, ΔV and ΔC represent the variation in absolute value of theparameters H, V and C, and C₀ represents the purity of the lock withrespect to which it is desired to evaluate the difference in colour.

The difference in colour, thus calculated and expressed by the ΔE,reflects the selectivity of the colourings, which decreases as the valueof the ΔE falls.

The results are given in the table below:

Colour Colour Selectivity of the obtained on obtained on colouringEXAMPLE natural hair permed hair ΔH ΔV ΔC ΔE 1 6.0P2.2/ 4.6P2.0/1.4 1.40.2 0.7 4.5 2.1 2 (*) 0.7P2.3/ 0.9P2.0/0.6 0.2 0.3 1.7 7.1 2.3

These results show that the colouring obtained by employing the dyeingcomposition in accordance with the invention of Example 1, that is tosay comprising the specific combination of2-chloro-6-methyl-3-aminophenol,2-(β-hydroxyethyloxy)-para-phenylenediamine and 2-methyl-5-aminophenol,is less selective than the colouring obtained by employing thecomposition of Example 2, which does not form part of the inventionbecause it comprises the combination of 2-chloro-6-methyl-3-aminophenol,2-(β-hydroxyethyl)-para-phenylenediamine and 2-methyl-5-aminophenol asdisclosed in Patent Application WO96/15765.

Comparative Dyeing Examples 3 and 4

The following dyeing compositions in accordance with the invention wereprepared (contents in grams):

EXAMPLE 3 4(*) 2-Chloro-6-methyl-3-aminophenol 0.588 0.588 (coupler)2-Aminomethyl-4-aminophenol 1.58  1.58  (oxidation base)meta-Aminophenol (coupler) 0.408 — Resorcinol (coupler) — 0.412 Commondyeing vehicle (**) (**) Demineralized water, q.s. for 100 g 100 g (*):Example not forming part of the invention (**) Common dyeing vehicle:

(*): Example not forming part of the invention

(**) Common dyeing vehicle:

It is identical to that used above for Examples 1 and 2.

At the time of use, each above dyeing composition was mixed with half anamount by weight of an oxidizing composition composed of a 10-volumeaqueous hydrogen peroxide solution (3% by weight).

Each resulting solution was applied for 30 minutes to locks of naturalgrey hair comprising 90% of white hairs and to locks of permed grey haircomprising 90% of white hairs. The locks of hair were subsequentlyrinsed, washed with a standard shampoo and then dried.

The colour of each lock of hair dyed with the compositions 3 and 4 wasevaluated in the Munsell system by means of a CM 2002 Minolta®calorimeter, in order to determine the selectivity of the colourings inthe same way as in the above Examples 1 and 2.

The results are given in the table below:

Colour Colour Selectivity of the obtained on obtained on colouringEXAMPLE natural hair permed hair ΔH ΔV ΔC ΔE 3 2.1YR3.5/ 0.9YR3.1/ 1.20.4 0.2 4.6 3.3 3.5 4 (*) 2.3YR3.7/ 0.8YR3.1/ 1.5 0.6 0.6 6.7 3.2 2.6

These results show that the colouring obtained by employing the dyeingcomposition in accordance with the invention of Example 3, that is tosay comprising the specific combination of2-chloro-6-methyl-3-aminophenol, 2-aminomethyl-4-aminophenol andmeta-aminophenol, is less selective than the colouring obtained byemploying the composition of Example 4, which does not form part of theinvention because it comprises the combination of2-chloro-6-methyl-3-aminophenol, 2-aminomethyl-4-aminophenol andresorcinol as disclosed in Patent Application WO96/15766.

Dyeing Examples 5 and 6

The following dyeing compositions in accordance with the invention wereprepared (contents in grams):

EXAMPLE 5 6 2-Chloro-6-methyl-3-aminophenol 0.235 0.235 (coupler)Pyrazolo[1,5-a]pyrimidine-3,7- 0.666 — diamine dihydrochloride(oxidation base) 4,5-Diamino-1-ethyl-3-methylpyrazole — 0.639dihydrochloride (oxidation base) 2,4-Diaminophenoxyethanol 0.361 —dihydrochloride (coupler) 1,3-Bis(2,4-diaminophenoxy)propane — 0.352tetrahydrochloride dihydrate (coupler) Common dyeing vehicle No. 2 —(***) Common dyeing vehicle No. 3 (****) — Demineralized water, q.s. for100 g 100 g (***) Common dyeing vehicle No. 2: 96° Ethanol 18 g Sodiummetabisulphite as a 35% aqueous 0.68 g solution Pentasodium salt of 1.1g diethylenetriaminepentaacetic acid Aqueous ammonia comprising 20% ofNH₃ 10 g (****) Common dyeing vehicle No. 3: 96° Ethanol 18 g Sodiummetabisulphite as a 35% aqueous 0.68 g solution Pentasodium salt of 1.1g diethylenetriaminepentaacetic acid K₂PO₄/KH₂PO₄ (1.5M/1M) buffer 10 g

At the time of use, each above dyeing composition was mixed with anequal amount by weight of an oxidizing composition composed of a20-volume aqueous hydrogen peroxide solution (6% by weight).

Each resulting composition was applied for 30 minutes to locks ofnatural grey hair comprising 90% of white hairs. The locks of hair weresubsequently rinsed, washed with a standard shampoo and then dried.

The shades obtained appear in the table below:

EXAMPLE DYEING pH SHADE OBTAINED 5 6.8 ± 0.2 Red mahogany 6  10 ± 0.2Deep purple

What is claimed is:
 1. A composition for the oxidation dyeing ofkeratinous fibres wherein said composition comprises, in a mediumsuitable for dyeing: at least one first coupler chosen from2-chloro-6-methyl-3-aminophenol and acid addition salts thereof; atleast one oxidation base; and at least one additional coupler chosenfrom meta-aminophenols and meta-phenylenediamines, wherein saidmeta-aminophenols are chosen from compounds of formula (V) and theiracid-addition salts:

in which: R₁₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical, R₂₀represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine and fluorine,R₂₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical, or a C₂-C₄ polyhydroxyalkoxyradical; with a first proviso that said composition does notsimultaneously include 2-(β-hydroxyethyly-para-phenylenediamine and2-methyl-5-aminophenol; with a second proviso that said composition doesnot simultaneously include 2-(β-hydroxyethyl)-para-phenylenediamine anda pyrimidine derivative; with a third proviso that said composition doesnot simultaneously include para-toluylenediamine and a pyridinederivative; and with a fourth proviso that said composition does notinclude a para-aminophenol.
 2. The composition of claim 1, wherein saidkeratinous fibers are human keratinous fibers.
 3. The composition ofclaim 2, wherein said human keratinous fibers are hair.
 4. Thecomposition of claim 1, wherein said at least one oxidation base ischosen from para-phenylenediamines, double bases, ortho-aminophenols andheterocyclic oxidation bases.
 5. The composition of claim 4, whereinsaid para-phenylenediamines are chosen from compounds of formula (I) andacid addition salts thereof:

in which: R₁ is chosen from a hydrogen atom, C₁-C₄ alkyl radicals, C₁-C₄monohydroxyalkyl radicals, C₂-C₄ polyhydroxyalkyl radicals,(C₁-C₄)alkoxy(C₁-C₄)alkyl radicals and C₁-C₄ alkyl radicals substitutedby a nitrogenous, phenyl or 4′-aminophenyl group; R₂ is chosen from ahydrogen atom, C₁-C₄ alkyl radicals, C₁-C₄ monohydroxyalkyl radicals,C₂-C₄ polyhydroxyalkyl radicals,(C₁-C₄)alkoxy(C₁-C₄)alkyl radicals andC₁-C₄ alkyl radicals substituted by a nitrogenous group; R₃ is chosenfrom a hydrogen atom, a halogen atom, C₁-C₄ alkyl radicals, C₁-C₄monohydroxyalkyl radicals, C₁-C₄ hydroxyalkoxy radicals, C₁-C₄acetylaminoalkoxy radicals, C₁-C₄ mesylaminoalkoxy radicals and C₁-C₄carbamoylaminoalkoxy radicals; R₄ is chosen from a hydrogen atom, ahalogen atom, and C₁-C₄ alkyl radicals.
 6. The composition of claim 5,wherein said nitrogenous group is chosen from amino radicals,mono(C₁-C₄)alkylamino radicals, di(C₁-C₄)alkylamino radicals,tri(C₁-C₄)alkylamino radicals, monohydroxy(C₁-C₄)alkylamino radicals,imidazolinium radicals and ammonium radicals.
 7. The composition ofclaim 5, wherein said para-phenylenediamines are chosen frompara-phenylenediamine, para-toluylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine,N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine,4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-3-methylaniline,4-amino-3-chloro-N,N-bis(β-hydroxyethyl)aniline,2-(β-hydroxyethyl)-para-phenylenediamine,2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine,N-(βhydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-(β-hydroxyethyloxy)-para-phenylenediamine,2-(β-acetylaminoethyloxy)para-phenylenediamine,N-(β-methoxyethyl)amino-para-phenylenediamine and acid addition saltsthereof.
 8. The composition of claim 4, wherein said double bases arecompounds comprising at least two aromatic nuclei containing aminoand/or hydroxyl groups.
 9. The composition of claim 4, wherein saiddouble bases are chosen from compounds corresponding to formula (II) andacid addition salts thereof

in which: Z₁ and Z₂, which are identical or different, are chosen from ahydroxyl radical and an —NH₂ radical which can be substituted by a C₁-C₄alkyl radical or by a connecting arm Y; the connecting arm Y is chosenfrom linear and branched alkylene chains comprising from 1 to 14 carbonatoms which can be interrupted or terminated by at least one entitychosen from nitrogenous groups and heteroatoms, and which is optionallysubstituted by at least one radical chosen from hydroxyl and C₁-C₆alkoxy radicals; R₅ and R₆ is chosen from a hydrogen atom, a halogenatom, C₁-C₄ alkyl radicals, C₁-C₄ monohydroxyalkyl radicals, C₂-C₄polyhydroxyalkyl radicals, C₁-C₄ aminoalkyl radicals and a connectingarm Y; R₇, R₈, R₉, R₁₀, R₁₁ and R₁₂, which are identical or different,are chosen from a hydrogen atom, a connecting arm Y and C₁-C₄ alkylradicals; and with the proviso that the compounds of formula (II) onlycomprise a single connecting arm Y per molecule.
 10. The composition ofclaim 9, wherein said at least one heteroatom is chosen from oxygen,sulphur and nitrogen atoms.
 11. The composition of claim 9, wherein saidnitrogenous groups are chosen from amino radicals, mono(C₁-C₄)alkylaminoradicals, di(C₁-C₄)alkylamino radicals, tri(C₁-C₄)alkylamino radicals,monohydroxy(C₁-C₄)alkylamino radicals, imidazolinium radicals andammonium radicals.
 12. The composition of claim 9, wherein said doublebases are chosen fromN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diamino-propanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)-tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-diethyl-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diaminophenoxy)3,5-dioxaoctane and acid addition saltsthereof.
 13. The composition of claim 4, wherein said ortho-aminophenolsare chosen from 2-aminophenol, 2-amino-5-methylphenol,2-amino-6-methylphenol, 5-acetamido-2-aminophenol and acid additionsalts thereof.
 14. The composition of claim 4, wherein said heterocyclicbases are chosen from pyridine derivatives, pyrimidine derivatives,pyrazole derivatives, pyrazolopyrimidine derivatives and acid additionsalts thereof.
 15. The composition of claim 14, wherein saidpyrazolopyrimidine derivatives are chosen from compounds of formula (IV)and acid addition and base addition salts thereof, and tautomeric formsthereof

in which: R₁₅, R₁₆, R₁₇ and R₁₈, which are identical or different, arechosen from a hydrogen atom, C₁-C₄ alkyl radicals, aryl radicals, C₁-C₄hydroxyalkyl radicals, C₂-C₄ polyhydroxyalkylradicals,(C₁-C₄)alkoxy(C₁-C₄)alkyl radicals, C₁-C₄ aminoalkyl radicals,it being possible for the amine to be protected by an acetyl, ureido orsulphonyl radical, (C₁-C₄)alkylamino(C₁-C₄)alkyl radicals,di((C₁-C₄)alkyl)amino(C₁-C₄)alkyl radicals, it being possible for thedialkyl radicals to form a carbonaceous ring or a heterocycle with 5 or6 ring members, hydroxy(C₁-C₄)alkylamino(C₁-C₄)alkyl radicals, anddi(hydroxy(C₁-C₄)alkyl)amino C₁-C₄)alkyl radicals; the X radicals, whichare identical or different, are chosen from a hydrogen atom, C₁-C₄ alkylradicals, aryl radicals, C₁-C₄ hydroxyalkyl radicals, C₂-C₄polyhydroxyalkyl radicals, C₁-C₄ aminoalkyl radicals,(C₁-C₄)alkylamino(C₁-C₄)alkyl radicals, di((C₁-C₄)alkyl)amino(C₁C₄)alkylradicals, it being possible for the dialkyls to form a carbonaceous ringor a heterocycle with 5 or 6 ring members,hydroxy(C₁-C₄)alkyl-amino(C₁-C₄)alkyl radicals, di(hydroxy(C₁-C₄alkyl)amino(C₁-C₄)alkyl radicals, amino radicals, (C₁-C₄)alkylamino radical,di(C₁-C₄ )alkyl)amino radicals, a halogen atom, carboxylic acid groupsand sulphonic acid groups; i has the value 0, 1, 2 or 3; p has the value0 or 1; q has the value 0 or 1; n has the value 0 or 1; with the provisothat: the sum p+q is other than 0; when p+q is equal to 2, then n hasthe value 0 and the NR₁₅R₁₆ and NR₁₇R₁₈ groups occupy the (2,3), (5,6),(6,7), (3,5) or (3,7) positions; when p +q is equal to 1, then n has thevalue 1 and the NR₁₅R₁₆ or NR₁₇R₁₈ group and the OH group occupy the(2,3), (5,6), (6,7), (3,5) or (3,7) positions.
 16. The composition ofclaim 15, wherein said compounds of formula (IV) are chosen frompyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;pyrazolo[1,5-a]pyrimidine-3,5-diamine;2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;3-aminopyrazolo[1,5-a]pyrimidin-7-ol;3-aminopyrazolo[1,5-a]pyrimidin-5-ol;2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol;2-((3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino)ethanol;2-((7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino)ethanol;5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5,N7,N7-tetramethylpyrazolo[1,5a]pyrimidine-3,7-diamine; and acid and baseaddition salts and their tautomeric forms, when there exists atautomeric equilibrium.
 17. The composition of claim 1, wherein saidcompounds of formula (V) are chosen from 5-amino-2-methoxyphenol,5amino-2-(β-hydroxyethyloxy)phenol, 5-amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-2-methylphenol,5-N-(β-hydroxyethyl)-amino4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 5-amino-4-chloro-2-methylphenol,5-amino-2,4-dimethoxy-phenol, 5-(γ-hydroxypropylamino)-2-methylphenoland acid addition salts thereof.
 18. The composition of claim 1, whereinsaid meta-phenylenediamines are chosen from compounds of formula (VI)and acid addition salts thereof:

in which: R₂₂ is chosen from a hydrogen atom, C₁-C₄ alkyl radicals,C₁-C₄ monohydroxyalkyl radicals and C₂-C₄ polyhydroxyalkyl radicals; R₂₃and R₂₄, which are identical or different, are chosen from a hydrogenatom, C₁-C₄ alkyl radicals, C₁-C₄ monohydroxyalkoxy radicals and C₂-C₄polyhydroxyalkoxy radicals; R₂₅ is chosen from a hydrogen atom, C₁-C₄alkoxy radicals, C₁-C₄ aminoalkoxy radicals, C₁-C₄ monohydroxyalkoxyradicals, C₂-C₄ polyhydroxy-alkoxy radicals and 2,4-diaminophenoxyalkoxyradicals.
 19. The composition of claim 18, wherein said compounds offormula (VI) are chosen from meta-phenylenediamine,3,5-diamino-1-ethyl-2-methoxybenzene,3,5-diamino-2-methoxy-1-methylbenzene, 2,4-diamino-1-ethoxybenzene,1,3-bis(2,4-diamino-phenoxy)propane, bis(2,4-diaminophenoxy)methane,1-(β-aminoethyloxy)-2,4-diaminobenzene,2-amino-1-(β-hydroxyethyloxy)-4-(methylamino)benzene,2,4-diamino-1-ethoxy-5-methylbenzene,2,4-diamino-5-(β-hydroxy-ethyloxy)-1-methylbenzene,2,4-diamino-1-(β,γ-dihydroxypropyloxy)benzene,2,4-diamino-1-(β-hydroxy-ethyloxy)benzene,2-amino-4-N-(β-hydroxyethyl)amino-1-methoxybenzene and acid additionsalts thereof.
 20. The composition of claim 1, wherein said at least onefirst coupler represents from 0.0001 to 5% by weight relative to thetotal weight of the dyeing composition.
 21. The composition of claim 20,wherein said at least one first coupler represents from 0.005 to 3% byweight relative to the total weight of the dyeing composition.
 22. Thecomposition of claim 1, wherein said at least one oxidation baserepresents from 0.0005 to 12% by weight relative to the total weight ofthe dyeing composition.
 23. The composition of claim 22, wherein said atleast one oxidation base represents from 0.005 to 6% by weight relativeto the total weight of the dyeing composition.
 24. The composition ofclaim 1, wherein said at least one additional coupler represents from0.0001 to 5% by weight relative to the total weight of the dyeingcomposition.
 25. The composition of claim 24, wherein said at least oneadditional coupler represents from 0.005 to 3%.
 26. The composition ofclaim 1, wherein said composition further comprises at least one directdye.
 27. The composition of claim 1, wherein said acid addition saltsare chosen from hydrochlorides, hydrobromides, sulphates and tartrates,lactates and acetates.
 28. The composition of claim 1, wherein saidmedium suitable for dyeing comprises water or a mixture of water and atleast one organic solvent chosen from lower C₁-C₄ alkanols, glycerol,glycols and glycol ethers, aromatic alcohols, and mixtures thereof. 29.The composition of claim 28, wherein said at least one organic solventis present in a proportion ranging from 1 to 40% by weight approximatelyrelative to the total weight of the dye composition.
 30. The compositionof claim 29, wherein said at least one organic solvent is present in aproportion ranging from 5 to 30%.
 31. The composition of claim 1,wherein said composition has a pH ranging from 3 to
 12. 32. Thecomposition of claim 31, wherein said pH ranges from 5 to
 11. 33. Thecomposition of claim 1, wherein said composition additionally containsat least one adjuvant chosen from anionic, cationic, nonionic,amphoteric and zwitterionic surfactants, anionic, cationic, nonionic,amphoteric and zwitterionic polymers, organic and inorganic thickeners,antioxidants, penetration agents, sequestrants, fragrances, buffers,dispersants, conditioners, film forming agents, ceramides, preservingagents and opacifiers.
 34. The composition of claim 1, wherein saidcomposition is in the form of a liquid, a cream, a gel or any other formappropriate for dyeing keratinous fibers.
 35. A method for dyeingkeratinous fibres, comprising contacting said fibres, for a timesufficient to achieve color development, with a dye compositioncomprising: at least one first coupler chosen from2-chloro-6-methyl-3-aminophenol and acid addition salts thereof; atleast one oxidation base; and at least one additional coupler chosenfrom meta-aminophenols and meta-phenylenediamines, wherein saidmeta-aminophenols are chosen from compounds of formula (V) and theiracid-addition salts:

in which: R₁₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical, R₂₀represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine and fluorine,R₂₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical, or a C₂-C₄ polyhydroxyalkoxyradical; with a first proviso that said dye composition does notsimultaneously include 2-(β-hydroxyethyl)-para-phenylenediamine and2-methyl-5-aminophenol; with a second proviso that said dye compositiondoes not simultaneously include 2-(β-hydroxyethyl)-para-phenylenediamineand a pyrimidine derivative; with a third proviso that said dyecomposition does not simultaneously include para-toluylenediamine and apyridine derivative; and with a fourth proviso that said dye compositiondoes not include a para-aminophenol; wherein said dye composition ismixed at the time of said contacting with an oxidizing compositioncomprising, in a medium suitable for dyeing, at least one oxidizingagent present in an amount sufficient for color development.
 36. Themethod of claim 35, wherein said keratinous fibers are human keratinfibers.
 37. The method of claim 36, wherein said human keratinous fibersare hair.
 38. The method of claim 35, wherein said time sufficientranges from 3 to 50 minutes.
 39. The method of claim 38, wherein saidtime sufficient ranges from 5 to 30 minutes.
 40. The method of claim 35,wherein said at least one oxidizing agent is chosen from hydrogenperoxide, urea peroxide, alkali metal bromates, persalts, and peracids.41. The method of claim 35, wherein said oxidizing composition includingthe oxidizing agent, after mixing with said dye composition, has a pHranging from 3 to
 12. 42. The method of claim 41, wherein said pH rangesfrom 5 to
 11. 43. The method of claim 35, wherein said oxidizingcomposition is contacted with said keratin fibers simultaneously orsequentially with said dye composition.
 44. The method of claim 35,wherein said oxidizing composition is contacted with said keratin fibersseparately from said dye composition.
 45. The method of claim 35,wherein said oxidizing composition additionally contains at least oneadjuvant chosen from anionic, cationic, nonionic, amphoteric andzwitterionic surfactants, anionic, cationic, nonionic, amphoteric andzwitterionic polymers, organic and inorganic thickeners, antioxidants,penetration agents, sequestrants, fragrances, buffers, dispersants,conditioners, film forming agents, ceramides, preserving agents andopacifiers.
 46. The method of claim 35, wherein said color developmentoccurs at an acidic, neutral or alkaline pH.
 47. The composition ofclaim 1, wherein said composition further comprises an oxidizingcomposition comprising, in a medium appropriate for dyeing, at least oneoxidizing agent present in an amount sufficient for color development ofsaid keratinous fibers.
 48. The composition of claim 47, wherein saidoxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkalimetal bromates, persalts, and peracids.
 49. The composition of claim 47,wherein the pH of said composition ranges from 3 to
 12. 50. Thecomposition of claim 49, wherein said pH ranges from 5 to
 11. 51. Thecomposition of claim 47, wherein said oxidizing composition additionallycontains at least one adjuvant chosen from anionic, cationic, nonionic,amphoteric and zwitterionic surfactants, anionic, cationic, nonionic,amphoteric and zwitterionic polymers, organic and inorganic thickeners,antioxidants, penetration agents, sequestrants, fragrances, buffers,dispersants, conditioners, film forming agents, ceramides, preservingagents and opacifiers.
 52. The composition of claim 49, wherein saidcomposition which is finally applied to keratinous fibres is in the formof a liquid, a cream, a gel, or any other form appropriate for carryingout dyeing of keratinous fibres.
 53. A multi-compartment dyeing deviceor kit for dyeing keratin fibers, comprising at least two compartments,wherein a first compartment contains a dye composition comprising atleast one first coupler chosen from 2-chloro-6-methyl-3-aminophenol andacid addition salts thereof; at least one oxidation base; and at leastone additional coupler chosen from meta-aminophenols andmeta-phenylenediamines, wherein said meta-aminophenols are chosen fromcompounds of formula (V) and their acid-addition salts:

in which: R₁₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical, R₂₀represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine and fluorine,R₂₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical, or a C₂-C₄ polyhydroxyalkoxyradical; with a first proviso that said dye composition does notsimultaneously include 2-(β-hydroxyethyl)-para-phenylenediamine and2-methyl-5-aminophenol; with a second proviso that said dye compositiondoes not simultaneously include 2-(β-hydroxyethyl)-para-phenylenediamineand a pyrimidine derivative; with a third proviso that said dyecomposition does not simultaneously include para-toluylenediamine and apyridine derivative; and with a fourth proviso that said dye compositiondoes not include a para-aminophenol; and a second compartment containsan oxidizing composition.
 54. A composition for the oxidation dyeing ofkeratinous fibres wherein said composition comprises, in a mediumsuitable for dyeing: at least one first coupler chosen from2-chloro-6-methyl-3-aminophenol and acid addition salts thereof; atleast one para-aminophenol of formula (III)

 in which: R₁₃ is chosen from a hydrogen atom, halogen atoms, C₁-C₄alkyl radicals, C₁-C₄ monohydroxyalkyl radicals,(C₁-C₄)alkoxy(C₁-C₄)alkyl radicals, C₁-C₄ aminoalkyl radicals andhydroxy(C₁-C₄)alkylamino(C₁-C₄)alkyl radicals; R₁₄ is chosen from ahydrogen atom and halogen atoms; with the proviso that at least one ofthe R₁₃ and R₁₄ radicals represents a hydrogen atom; and at least oneadditional coupler chosen from meta-aminophenols andmeta-phenylenediamines, wherein said meta-aminophenols are chosen fromcompounds of formula (V) and their acid-addition salts:

 in which: R₁₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, aC₁-C₄ monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical, R₂₀represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine and fluorine,R₂₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical, or a C₂-C₄ polyhydroxyalkoxyradical; with a first proviso that said composition does notsimultaneously include 2-(β-hydroxyethyl)-para-phenylenediamine and2-methyl-5-aminophenol; with a second proviso that said composition doesnot simultaneously include 2-(β-hydroxyethyl)para-phenylenediamine and apyrimidine derivative; and with a third proviso that said compositiondoes not simultaneously include para-toluylenediamine and a pyridinederivative.
 55. The composition of claim 54, wherein saidpara-aminophenols are chosen from para-aminophenol,4-amino-3-fluorophenol, 4-amino-2-methylphenol,4-amino-2-(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol,4-amino-2-(aminomethyl)-phenol,4-amino-2-((β-hydroxyethyl)aminomethyl)phenol, 4-amino-2-fluorophenoland acid addition salts thereof.
 56. A method for dyeing keratinousfibres, comprising contacting said fibres, for a time sufficient toachieve color development, with a dye composition comprising: at leastone first coupler chosen from 2-chloro-6-methyl-3-aminophenol and acidaddition salts thereof; at least one para-aminophenol of formula (III)

 in which: R₁₃ is chosen from a hydrogen atom, halogen atoms, C₁-C₄alkyl radicals, C₁-C₄ monohydroxyalkyl radicals,(C₁-C₄)alkoxy(C₁-C₄)alkyl radicals, C₁-C₄ aminoalkyl radicals andhydroxy(C₁-C₄)alkylamino(C₁-C₄)alkyl radicals; R₁₄ is chosen from ahydrogen atom and halogen atoms; with the proviso that at least one ofthe R₁₃ and R₁₄ radicals represents a hydrogen atom; and at least oneadditional coupler chosen from meta-aminophenols andmeta-phenylenediamines, wherein said meta-aminophenols are chosen fromcompounds of formula (V) and their acid-addition salts:

 in which: R₁₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, aC₁-C₄ monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical, R₂₀represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine and fluorine,R₂₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical, or a C₂-C₄ polyhydroxyalkoxyradical; with a first proviso that said composition does notsimultaneously include 2-(β-hydroxyethyl)-para-phenylenediamine and2-methyl-5-aminophenol; with a second proviso that said composition doesnot simultaneously include 2-(β-hydroxyethyl)para-phenylenediamine and apyrimidine derivative; and with a third proviso that said compositiondoes not simultaneously include para-toluylenediamine and a pyridinederivative; wherein said dye composition is mixed at the time of saidcontacting with an oxidizing composition comprising, in a mediumsuitable for dyeing, at least one oxidizing agent present in an amountsufficient for color development.
 57. A multi-compartment dyeing deviceor kit for dyeing keratin fibers, comprising at least two compartments,wherein a first compartment contains a dye composition comprising atleast one first coupler chosen from 2-chloro-6-methyl-3-aminophenol andacid addition salts thereof; at least one para-aminophenol of formula(III)

 in which: R₁₃ is chosen from a hydrogen atom, halogen atoms, C₁-C₄alkyl radicals, C₁-C₄ monohydroxyalkyl radicals,(C₁-C₄)alkoxy(C₁-C₄)alkyl radicals, C₁-C₄ aminoalkyl radicals andhydroxy(C₁-C₄)alkylamino(C₁-C₄)alkyl radicals; R₁₄ is chosen from ahydrogen atom and halogen atoms; with the proviso that at least one ofthe R₁₃ and R₁₄ radicals represents a hydrogen atom; and at least oneadditional coupler chosen from meta-aminophenols andmeta-phenylenediamines, wherein said meta-aminophenols are chosen fromcompounds of formula (V) and their acid-addition salts:

 in which: R₁₉ represents a hydrogen atom, a C₁-C₄ alkyl radical, aC₁-C₄ monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical, R₂₀represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine and fluorine,R₂₁ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄ alkoxyradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ monohydroxyalkoxy radical, or a C₂-C₄ polyhydroxyalkoxyradical; with a first proviso that said composition does notsimultaneously include 2-(β-hydroxyethyl)-para-phenylenediamine and2-methyl-5-aminophenol; with a second proviso that said composition doesnot simultaneously include 2-(β-hydroxyethyl)-para-phenylenediamine anda pyrimidine derivative; and with a third proviso that said compositiondoes not simultaneously include para-toluylenediamine and a pyridinederivative; and a second compartment contains an oxidizing composition.